Multifunctional magnetic composites based in meta-magnetic shape memory alloys for 3D printing applications

Magnetostructural coupling, which is the coincidence of crystallographic and magnetic transition, has obtained intense attention for its abundant magnetoresponse effects and promising technological applications, such as solid-state refrigeration, magnetic actuators and sensors. The hexagonal Ni2In-type compounds have attracted much attraction due to the strong magnetostructural coupling and the resulted giant negative thermal expansion and magnetocaloric effect. However, the as-prepared samples are quite brittle and naturally collapse into powders. Here, we report the effect of particle size on the magnetostructural coupling and magnetocaloric effect in the Ni2In-type Mn-Fe-Ni-Ge compound, which undergoes a large lattice change across the transformation from paramagnetic austenite to ferromagnetic martensite. The disappearance of martensitic transformation in a large amount of austenitic phase with reducing particle size, to our best knowledge, has not been reported up to now. The ratio can be as high as 40.6% when the MnNi0.8Fe0.2Ge bulk was broken into particles in the size range of 5~15 μm. Meanwhile, the remained magnetostructural transition gets wider and the magnetic hysteresis becomes smaller. As a result, the entropy change drops, but the effective cooling power RCeffe increases and attains to the maximum at particles in the range of 20~40 μm. These observations provide constructive information and highly benefit practical applications for this class of novel magnetoresponse materials.

Heusler-type Ni-Mn-based metamagnetic shape memory alloys (MetaMSMAs) are promising candidates for magnetic refrigeration. To increase heat exchange rate and efficiency of cooling, the material should have a high surface/volume ratio. In this work, the typical Ni50Mn35In15 MetaMSMA was selected to fabricate thin ribbons by melt-spinning. The characteristic transformations of the ribbons were determined by calorimetry, X-ray diffraction, scanning electron microscopy and thermomagnetization measurements. The inverse and conventional magnetocaloric effects (MCEs) associated with the martensitic transformation (MT) and the ferromagnetic transition of the austenite (TCA), respectively, were measured directly by the adiabatic method (ΔTad) and indirectly by estimating the magnetic entropy change from magnetization measurements. It is found that the ribbons exhibit large values of ΔTad = −1.1 K at μ0ΔH = 1.9 T, in the vicinity of the MT temperature of 300 K for inverse MCE, and ΔTad = 2.3 K for conventional MCE at TCA = 309 K. This result strongly motivates further development of different MetaMSMA refrigerants shaped as ribbons.

Magnetic response of porous NiCoMnSn metamagnetic shape memory alloys fabricated using solid-state replication

Bulk-like first-order magnetoelastic transition in FeRh particles

Particle size plays an important role in the electrochemical performance of cathodes for lithium-ion (Li-ion) batteries. High energy planetary ball milling of LiNi1/3Mn1/3Co1/3O2 (NMC) cathode materials was investigated as a route to reduce the particle size and improve the electrochemical performance. The effect of ball milling times, milling speeds, and composition on the structure and properties of NMC cathodes was determined. X-ray diffraction analysis showed that ball milling decreased primary particle (crystallite) size by up to 29%, and the crystallite size was correlated with the milling time and milling speed. Using relatively mild milling conditions that provided an intermediate crystallite size, cathodes with higher capacities, improved rate capabilities, and improved capacity retention were obtained within 14 μm-thick electrode configurations. High milling speeds and long milling times not only resulted in smaller crystallite sizes but also lowered electrochemical performance. Beyond reduction in crystallite size, ball milling was found to increase the interfacial charge transfer resistance, lower the electrical conductivity, and produce aggregates that influenced performance. Computations support that electrolyte diffusivity within the cathode and film thickness play a significant role in the electrode performance. This study shows that cathodes with improved performance are obtained through use of mild ball milling conditions and appropriately designed electrodes that optimize the multiple transport phenomena involved in electrochemical charge storage materials.

Different applications based on metamagnetic shape memory alloy (MSMA) require monitoring the evolution of the martensitic transformation (MT) to optimize the actuation mechanism. To avoid interaction with the active material, a non-contact technique would be ideal. Nevertheless, non-contact detection involves complex methods like diffraction, optical analysis, or electromagnetic technology. The present work demonstrates that the MT can be monitored without interaction with the active material using a low-cost technology based on the Giant Magnetoimpedance (GMI) effect. The GMI sensor is based on a (CoFe)SiB soft magnetic wire submitted to an alternating current and whose second harmonic voltage variation allows to detect changes in the strength of the stray magnetic fields linked to the metamagnetic phase transition. The sensor has been tested using the MT of a NiMnInCo MSMA. A specific application for environmental temperature control using the non-contact GMI sensor is proposed.

Improving mechanical properties of nano-sized TiC particle reinforced AA7075 Al alloy composites produced by ball milling and hot pressing

The influences of Gd concentration on martensitic transformation and magnetic properties of NiMnIn alloys were investigated by differential scanning calorimetry (DSC) , vibrating sample magnetometry (VSM), X-ray diffraction (XRD) and etc. It shows that addition of Gd enhances martensite transition temperature and that X-ray diffraction analysis of experimental alloys is revealed which the mixture is martensite and austenite at room temperature. These alloys show promise as a metamagnetic shape memory alloy with magnetic-field-induced shape memory effect.

We show that in metamagnetic shape memory alloys exhibiting a magnetostructural first order phase transition the direct transition from ferromagnetic austenite to nonmagnetic martensite is isothermal. In contrast to the direct transformation, the reverse one (nonmagnetic martensite–ferromagnetic austenite) is athermal, just as are athermal both direct and reverse martensitic transformations in conventional ferromagnetic shape memory alloys. The observed asymmetry of properties of the direct and reverse phase transitions in metamagnetic alloys, together with the data on entropy change during the magnetostructural transition, evidences that the magnetostructural transition is driven by the first order lattice modification. The change in magnetic ordering is an effect accompanying the lattice modification, opposing the direct transformation and promoting the reverse one. It has been shown that relaxation effects in metamagnetic shape memory alloys are intrinsic in the direct transformation itself and do not require the “arrest” of the transformation.

Direct measurement of large reversible magnetic-field-induced strain in Ni–Co–Mn–In metamagnetic shape memory alloys

Ni/YSZ composites for a cathode that can be used in high temperature electrolysis were prepared by ball milling of Ni and YSZ powder. Ball milling was performed in a dry process and in ethanol. The microstructure and electrical conductivity of the composites were examined by XRD, SEM, TEM and a 4-point probe. XRD patterns for both the dry and wet ball-milled powders showed that the composites were composed of crystalline Ni and YSZ particles. The patterns did not change with increases in the milling time up to 48 h. Dry-milling slightly increased the average particle size compared to starting Ni particles, but little change in theparticle size was observed with the increase in milling time. On the other hand, the wet-milling reduced the average size and the increasing milling time induced a further decrease in the particle size. After cold-pressing and annealing at 900 oC for 2 h, the dry-milled powder exhibited high stability against Ni sintering so that the particle size changed little, but the particle size increased in the wet-milled powder. The electrical conductivity increased after sintering at 900 oC. Particles from the dry and wet process became denser and contacted closer after sintering, providing better electron migration paths.

Commercial wood flour of pine (Pinus densiflora) was used as an experimental material. It was milled with different milling times 0, 10, 20, 30, 40, 60, and 120 min to investigate the effect of their particle size distribution on the mechanical properties of the wood–plastic composite. Two kinds of drying conditions, 7 days of freeze-drying at a temperature of −45 °C and heat drying (80 °C) for 24 h were applied. Polypropylene and maleic anhydride-grafted polypropylene were used as a matrix and the compatibilizer of the wood–plastic composite compound, respectively. Particle size analysis showed that an increase in the time of ball milling decreased the wood flour size. However, an excessive milling period of time longer than 40 min corresponded to an increase in the amount of aggregation. Scanning electron microscope images showed the existence of aggregation for the wood flour with 120 min of wet milling time. As the particle size decreased, mechanical properties of wood–plastic composite increased for up to 30 min of wet milling time and then slightly decreased. This behavior might be due to aggregation. The optimum mechanical property was obtained at 30 min of wet milling time under freeze-drying conditions.

Dynamic magnetic characteristics during martensitic transformations in NiMnInCo metamagnetic shape memory alloy

Mechanical alloying of Al‐Ti was performed by high‐energy ball milling at ambient temperature under argon atmosphere. A Fritsch Pulverisette‐5 planetary type ball mill was used for the mechanical alloying for 2 up to 30 hours with the ball milling size of 15 mm and the rotational speed of about 360 rpm. The balls‐to‐powder ratio was 20 : 1 (in weight percent). The final products have been characterized by SEM and XRD. The SEM results showed that the average particle size of mechanically alloyed Al‐Ti powders decreased with increasing milling time and the particle size was smaller than 1.63 μm after 30 hours milling. The XRD results showed that the crystallite size of mechanically alloyed Al‐Ti powders decreased with increasing milling time and the steady‐state crystallite size was approximately 17.6 nm. It also found that the peaks of Ti begin disappear with the increasing of milling time, which indicates the forming alloying of Ti atoms in the Al matrix. The SEM results confirmed that the nanocrystalline produced were binary alloy of Al‐Ti and no other impurities detected in the particles. The optimum milling time for the mechanical alloying of nanocrystalline Al‐Ti was 30 hours.

Milling amorphous FeSiB ribbons with vibratory ball and disc mills